Optical waveguide and method of manufacture

ABSTRACT

An optical waveguide capable of having various characteristics and a method of manufacture thereof as well as a method of manufacturing a crystal film are provided. An optical functional material KTa x Nb 1-x O 3  is used as an optical waveguide. The input optical signal is transmitted to the KTa x Nb 1-x O 3  film. The KTa x Nb 1-x O 3  film undergoes changes in optical property when an external voltage signal-is applied to the electrode. Therefore, as it passes through the KTa x Nb 1-x O 3  film, the input optical signal is modulated by the characteristic change. The modulated optical signal is taken out as an output optical signal.

This application is based on Japanese Patent Application Nos.2001-143570 filed May 14, 2001, 2001-143571 filed May 14, 2001,2001-146560 filed May 16, 2001 and 2001-165283 filed May 31, 2001, thecontents of which are incorporated hereinto by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an optical waveguide and a method ofmanufacture thereof and more particularly to an optical waveguide fornovel functional optical integrated circuits using an optical functionalmaterial KTa_(x)Nb_(1-x)O₃ as the optical waveguide and a method ofmanufacture thereof and also to a method of manufacturing a crystal filmfor use with optical communication devices.

2. Description of the Related Art

Intensive research and development efforts are being made from a costperformance point of view to develop optical integrated circuits thatintegrate on a single substrate optical devices that perform emission,detection, modulation, and multiplexing and demultiplexing of light.This integration technology is expected to reduce electric power,enhance performance and reduce cost of these optical devices.

Conventional optical integrated circuits currently in wide use have afabrication in which a waveguide structure is formed on a semiconductorsubstrate using SiO₂ and polymers to process an optical signal launchedfrom outside. The waveguide structure refers to a structure comprisingan undercladding layer, a waveguide layer formed on the undercladdinglayer and having a refractive index higher than that of theundercladding layer, and an overcladding layer covering the waveguidelayer and having a refractive index smaller than that of the waveguidelayer. To realize a function of optical signal processing, theconventional optical ICs change an optical properties of the waveguidematerial as represented by ordinary and extraordinary refractive indicesby applying external fields, such as heat, electric fields, magneticfields and sound, thereby achieving such functions asmultiplexing/demultiplexing optical signals and adjusting a transfertime.

However, since the waveguide materials currently available are limitedto SiO₂, polymers, semiconductors and a small range of nonlinearcrystals, the changing of the optical properties as realized by themethod described above is greatly restricted by the characteristic ofthe waveguide material used, thus imposing limitations on the applicableoptical signal processing.

Under these circumstances, the use of a novel waveguide materialKTa_(x)Nb_(1-x)O₃ is being considered. The optical functional materialKTa_(x)Nb_(1-x)O₃ exhibits an optical second-order nonlinear effect. Anoptical nonlinear constant of this material is 1,200-8,000 pm/V,significantly larger than 31 pm/V which is an optical nonlinear constantof LiNbO₃ for example.

Further, since this optical nonlinear effect is attributed to thedisplacement of positions of constitutional elements by the applicationof an electric field, the presence or absence of the optical nonlineareffect can be controlled by the application of an electric field.

The material KTa_(x)Nb_(1-x)O₃ undergoes a ferroelectric phasetransition at a composition-dependent Curie temperature of between −250°C. and 400° C. At this Curie temperature as a boundary the material'sproperty changes significantly. For example, its dielectric constantgreatly changes from approximately 3,000 to about 20,000. It is possibleto create a new optical integrated circuit taking advantage of theferroelectric phase transition. The Curie temperature varies dependingon the composition x of KTa_(x)Nb_(1-x)O₃, and adding Li toKTa_(x)Nb_(1-x)O₃ to produce K_(y)Li_(1-y)Ta_(x)Nb_(1-x)O₃ makes itpossible to adjust the temperature range.

The fabrication process of an optical waveguide requires steps of firstforming a waveguide material film and then performing patterning andetching on the film using photolithography or the like.

The currently used waveguide materials, however, are limited to SiO₂,polymers, semiconductors and a small range of nonlinear crystals. Hence,the modification of optical properties as realized by the aforementionedapplication of heat, electric fields, magnetic fields or sound isgreatly restricted by the characteristics of the waveguide materialused. The conventional optical ICs therefore have a problem that theapplicable range of optical signal processing is very narrow.

Further, the method of manufacturing an optical waveguide using theKTa_(x)Nb_(1-x)O₃ optical functional material described above alsorequires the fabrication process, similar to the conventional one, offorming a film of the waveguide material and patterning the waveguidefilm by photolithography. Therefore, even in using the novel waveguidematerial KTa_(x)Nb_(1-x)O₃, the conventional technology has a problemthat the waveguide fabrication process is complex.

Another problem is that, although the waveguide fabrication is essentialin obtaining a desired performance, a technique to form waveguides in aKTN crystal has not yet been established. This is attributed to the factthat ions that increase the refractive index and still do not degradethe nonlinear characteristic after diffusion has not been found.

The chemical vapor deposition (CVD) method vaporizes a materialcontaining constitutional components and causes a desired reaction in agas phase or on a substrate. Forming a waveguide material film by usingthe CVD method requires a volatile compound containing theconstitutional components. In KTN or KLTN, as to the compounds of Ta andNb, halide and alkoxide have high volatility and can be used as thestarting material when the CVD method is applied.

As to K and Li compounds, there is not much information available aboutthe materials which provide sufficient vapor pressures. In the case of Kin particular, no material has been known which is effective for usewith the CVD method. The essential reason for this is that alkali metalelements such as K and Li tend to be ionized easily and cannot easily bekept in a molecular state necessary for vaporization.

SUMMARY OF THE INVENTION

The present invention has been accomplished to overcome these problemsand provide an optical waveguide and a method of manufacture thereof,the optical waveguide being capable of having a variety ofcharacteristics not achievable with conventional devices and of forminga waveguide easily.

Another object of this invention is to provide a diffused waveguide anda method of manufacture thereof, the diffused waveguide allowing a KTNcrystal to be formed into a waveguide by diffusing Li, a technique notachievable with conventional devices.

To achieve these objective, the present invention provides an opticalwaveguide comprising: an undercladding layer; a waveguide layer formedon the undercladding layer and having a higher refractive index thanthat of the undercladding layer; and an overcladding layer covering thewaveguide layer and having a lower refractive index than that of thewaveguide layer; wherein the undercladding layer is a substrate and thewaveguide layer is formed from an optical functional materialKTa_(x)Nb_(1-x)O₃ (0<x<1).

Further, the substrate is one of a KTa_(y)Nb_(1-y)O₃ (O≦y≦1, y≠x)substrate, a MgO substrate, a MgAl₂O₄ substrate and a NdGaO₃ substrate.

Further, the undercladding layer comprises the substrate and one ofSiO₂, KTa_(z)Nb_(1-x)O₃ (0≦z≦1, z≠x), MgO, MgAl₂O₄ and NdGaO₃ depositedon the substrate.

Further, the overcladding layer is formed from one of KTa_(u)Nb_(1-u)O₃(0≦u≦1, u≠x), MgO, MgAl₂O₄, NdGaO₃ and polymer.

Further, an optical waveguide comprises: an undercladding layer; awaveguide layer formed on the undercladding layer and having a higherrefractive index than that of the undercladding layer; and anovercladding layer covering the waveguide layer and having a lowerrefractive index than that of the waveguide layer; wherein theundercladding layer is a substrate and the waveguide layer is formedfrom an optical functional material K_(1-v)Li_(v)Ta_(x)Nb_(1-x)O₃(0<x<1, 0<v≦0.5).

This invention is characterized in that the optical waveguide is formedfrom an optical functional material KTa_(x)Nb_(1-x)O₃ whose opticalproperties represented by an electrooptical effect (EO effect), anacoustooptic effect (AO effect) and a figure of merit are remarkablylarge when compared with those of conventional waveguide materials.

The optical functional material KTa_(x)Nb_(1-x)O₃ is a paraelectriccrystal material and has a cubic structure with a refractive index of2.4 at temperature higher than ferroelectric transition. When anexternal field is applied in the crystal axis direction, the resultingpositional displacement of the constitutional elements produces anoptical second-order nonlinear effect. The optical nonlinearity constantof this optical functional material is 1,200-8,000 pm/V, significantlylarger than, for example, 31 pm/V which is the optical nonlinearityconstant of LiNbO₃.

The optical nonlinear effect is the result of the positionaldisplacement of constitutional elements caused by the application of anelectric field. Hence, the presence or absence of the optical nonlineareffect can be controlled by the application of an electric field. Thematerial KTa_(x)Nb_(1-x)O₃ undergoes a ferroelectric phase transition ata composition-dependent Curie temperature of between −250° C. and 400°C. At this Curie temperature as a boundary the material's propertychanges sharply. For example, its dielectric constant greatly changesfrom approximately 3,000 to about 20,000. It is therefore possible tocreate a new optical integrated circuit taking advantage of opticalcharacteristic changes caused by the ferroelectric phase transition.

The Curie temperature varies depending on the composition x ofKTa_(x)Nb_(1-x)O₃, and adding Li to KTa_(x)Nb_(1-x)O₃ can adjust itsCurie temperature range.

Further, this invention provides a method of manufacturing an opticalwaveguide, wherein the optical waveguide comprises an undercladdinglayer, a waveguide layer formed on the undercladding layer and having ahigher refractive index than that of the undercladding layer, and anovercladding layer covering the waveguide layer and having a lowerrefractive index than that of the waveguide layer, the method comprisingsteps of: using the undercladding layer as a substrate and forming onthe substrate a structure constituting a crystal growth nucleationposition; and growing a thin film of an optical functional materialKTa_(x)Nb_(1-x)O₃ (0<x<1) into a rectangular parallelepiped with thestructure as a center to form the waveguide layer.

Further, this invention provides a method of manufacturing an opticalwaveguide, wherein the optical waveguide comprises an undercladdinglayer, a waveguide layer formed on the undercladding layer and havinga-higher refractive index than that of the undercladding layer, and anovercladding layer covering the waveguide layer and having a lowerrefractive index than that of the waveguide layer, the method comprisingthe steps of: using the undercladding layer as a substrate and formingon the substrate a structure constituting a crystal growth nucleationposition; and growing a thin film of an optical functional materialK_(1-y)Li_(y)Ta_(x)Nb_(1-x)O₃ (0<x<1, 0<y≦0.5) into a rectangularparallelepiped with the structure as a center to form the waveguidelayer.

An ordinary waveguide fabrication process involves depositing a film ofthe material for a waveguide layer over a large area and then patterningthe film into a desired configuration of the waveguide rectangular incross section by photolithography. This invention takes advantage of thefact that the waveguide material is KTa_(x)Nb_(1-x)O₃ crystal and,instead of the ordinary process described above, forms the opticalwaveguide rectangular in cross section in a single film making step.

The optical waveguide fabrication method of this invention requiresdepositing a thin film of KTa_(x)Nb_(1-x)O₃ with optical characteristicssufficient for light propagation, i.e., satisfactory crystal qualitythat produces such characteristics, and then forming the film into apredetermined structure at a predetermined location according to adesign of the optical integrated circuit. Such an optical quality can berealized by a crystal epitaxial growth method. In a field ofsemiconductor crystal growth technology, an epitaxial growth methodavailable that grows thin films having a high degree of lattice mismatchbetween a substrate and a thin film, as in the case of GaN-on-sapphireand GaAs-on-Si, is a micro-channel epitaxy (for example, T. Nishinagaand H. J. Scheel, “Advances in Superconductivity VIII,” ed. By H.Hayakawa and Y. Enomoto (Springer-Verlag, Tokyo, 1996) p. 33). Thismicro-channel epitaxy controls the thin film growth nucleation positionby a groove formed on the upper surface of a seed layer on the substrateand improves the crystal quality of the thin film by the horizontalgrowth of the thin film from the nucleation position.

In this invention, since the nucleation position and the thin filmgrowth direction can be controlled, when the crystal material has astrong crystal habit, it is possible to create a structure enclosed bythe singular faces of the crystal material. The KTa_(x)Nb_(1-x)O₃crystal material used in this invention has a cubic crystal structureand a strong crystal habit which is constructed by the {100} singularfaces, so that a rectangular thin film enclosed by the {100} planes islikely to grow. In the process of growing a thin film, the growth nucleion the substrate are generated starting from where the surface energy ofthe substrate is smallest. When there are holes or grooves on a planarsubstrate, the areas of the holes or grooves have side surfaces inaddition to the bottom surfaces, increasing the number of contactsurfaces with which the material supplied onto the substrate comes intocontact. It is apparent also from the classical theory of crystal growththat an increase in the number of contact surfaces lowers the surfaceenergy of the areas of the holes or grooves and thus the probability ofcrystal nuclei being generated in these areas becomes higher than inother planar areas.

Therefore, by forming in advance holes or grooves in that substratecontact surface where a rectangular waveguide is to be formed, theKTa_(x)Nb_(1-x)O₃ crystal material can be made to start growing a thinfilm at the holes or grooves as the growth nucleation points and fillthese holes or grooves. If the growth of the KTa_(x)Nb_(1-x)O₃ crystalmaterial is continued, a growth in the horizontal direction of thesubstrate, i.e., along the free surface, also starts, in addition to thegrowth in the vertical direction of the substrate at the holes orgrooves. At this time, as to the growth in the horizontal direction ofthe substrate, the film being grown is limited in shape by the {100}singular faces of the KTa_(x)Nb_(1-x)O₃ crystal material. Thus, a filmof KTa_(x)Nb_(1-x)O₃ having a rectangular parallelepiped structureenclosed by {100} planes can be produced.

Further, this invention provides a diffused waveguide formed bydiffusing ions in a crystal and using as a waveguide core an area of thecrystal diffused with the ions and having a higher refractive index thanthose of surrounding areas, wherein the crystal has a composition ofKTa_(1-x)Nb_(x)O₃ and the ions are Li.

Further, this invention forms a waveguide core with a higher refractiveindex than those of the surrounding areas by diffusing Li ions in thecrystal of a composition of KTa_(1-x)Nb_(x)O₃.

That is, this invention is characterized by Li ions being diffused inthe KTN crystal to form a core with a high refractive index. Li ions canbe thermally diffused by substituting a K site and the KLTN crystalhaving the composition of K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ also has aperformance equal to or higher than that of the KTN crystal. Therefore,there is no possibility of characteristic degradation due to iondiffusion. Further, the relative index difference obtained by adding Lithrough thermal diffusion is 2% or higher, which is sufficient for thefabrication of a waveguide. This means that Li is an appropriate ion forforming waveguide. The melt containing LiNO₃ used for diffusion has alow melting point of 261° C., which means that a stable melt can beobtained easily. This melt has a high water solubility so that, afterthe diffusion processing, it can be easily washed away with water. Thus,it has no adverse effects on the subsequent thermal diffusion processingin a gas.

As described above, the manufacture of a diffused waveguide using Liions has-advantages that it can control the refractive index withoutdegrading its characteristics and that the diffusion process using LiNO₃is simple and can perform diffusion at low temperatures.

Further, this invention provides a method of manufacturing a crystalfilm having a composition of KTa_(1-x)Nb_(x)O₃ (0<x<1), the methodcomprising steps of: introducing, in the form of gas flows into areaction system having a substrate, β-diketone complex of K (R is analkyl group with a carbon number of 1 to 7, R′ is an alkyl group orC_(n)F_(2n+1), and n is 1 to 3) expressed by a general formula (1) as afirst initial material component,

at least one of a gaseous Ta compound and a volatile Ta compound as asecond initial material component, at least one of a gaseous Nb compoundand a volatile Nb compound as a third initial material component, and anoxygen-containing gas used as an oxidizer, and reacting these componentsin a gas phase or on the substrate to form a crystal ofKTa_(1-x)Nb_(x)O₃ on the substrate.

The above and other objects, effects, features and advantages of thepresent invention will become more apparent from the followingdescription of embodiments thereof taken in conjunction with theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view showing an example fabrication of anoptical waveguide applying the present invention;

FIG. 2 is a perspective view showing another example fabrication of anoptical waveguide applying the present invention;

FIG. 3 is a perspective view showing a substrate formed with a groove asa crystal growth nucleation position for a KTa_(x)Nb_(1-x)O₃ crystal;

FIG. 4 is a perspective view showing a substrate formed with holes ascrystal growth nucleation positions for KTa_(x)Nb_(1-x)O₃ crystals;

FIG. 5 is a perspective view showing a substrate having an electrodelayer formed with holes as crystal growth nucleation positions forKTa_(x)Nb_(1-x)O₃ crystals;

FIG. 6 is a cross-sectional view taken along the line VI-VI of FIG. 5;

FIG. 7 is a graph showing a SIMS analysis result of a Li iondistribution in Embodiment 3-1;

FIG. 8 is a graph showing a SIMS analysis result of a Li iondistribution after an internal diffusion in Embodiment 3-1;

FIG. 9 is a graph showing a refractive index distribution after aninternal diffusion of Li ions in. Embodiment 3-1;

FIG. 10 illustrates a cross-sectional view of a waveguide after arediffusion of K, and a diagram showing a SIMS analysis result of a Liion distribution in Embodiment 3-2;

FIG. 11 is a perspective view showing a fabrication of a wavelengthconversion device in Embodiment 3-3;

FIG. 12 is a diagram showing a wavelength conversion spectrum inEmbodiment 3-4 and Embodiment 4-14;

FIG. 13 is a schematic diagram of a film deposition apparatus inEmbodiment 4-1;

FIG. 14 is a graph showing a measurement result of a dielectric constantof a KTN film fabricated in Embodiment 4-1;

FIG. 15 is a graph showing a measurement result of a dielectric constantof a KLTN film fabricated in Embodiment 4-13;

FIG. 16A is a perspective view of a wavelength conversion devicefabricated in Embodiment 4-14; and

FIG. 16B is a cross-sectional view of the wavelength conversion devicetaken along the line XVIB-XVIB of FIG. 16A.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Embodiments of the present-invention will be described in detail. Inrealizing an optical waveguide of this invention it is necessary todeposit a thin film of KTa_(x)Nb_(1-x)O₃ having an satisfactory opticalcharacteristic or crystal quality for lightwave propagation and form itinto a desired structure at a predetermined location according to adesign of an optical integrated circuit. The process of manufacturing anoptical waveguide according to the present invention can be classedlargely into four basic processes:

1) Forming a KTa_(x)Nb_(1-x)O₃ thin film on a substrate;

2) Manufacturing a waveguide layer by processing the KTa_(x)Nb_(1-x)O₃thin film;

3) Manufacturing a mechanism for applying external fields to theKTa_(x)Nb_(1-x)O₃ waveguide layer; and

4) Manufacturing a cover layer over the KTa_(x)Nb_(1-x)O₃ waveguidelayer.

These four manufacturing processes are referred to as a manufacturingprocess 1, a manufacturing process 2, a manufacturing process 3 and amanufacturing process 4 respectively and will be explained in thefollowing.

The order of these four manufacturing processes is determined accordingto a design structure of the optical integrated circuit. In addition,the determination of this order takes into account whether a materialregion already fabricated by one manufacturing process may or may not bedegraded in quality by the subsequent manufacturing process. Hence, itshould be noted that the actual order of the manufacturing processesdoes not necessarily agree with the order indicated by the accompanyingnumbers.

Since the waveguide layer material is KTa_(x)Nb_(1-x)O₃, the materialsforming the substrate and the cover layer need to have a sufficientrefractive index difference with respect to the refractive index ofKTa_(x)Nb_(1-x)O₃ to confine light in the waveguide layer.

Embodiment 1

FIG. 1 is a perspective view showing the fabrication of an opticalwaveguide applying the present invention. A basic fabrication shown hereas an example waveguide structure for explanation uses a ridge typeoptical waveguide as an optical waveguide and an electric fieldapplication from an electrode as an external field applicationmechanism. In the figure, reference number 1 represents a substrate thatfunctions as an undercladding layer, 2 a waveguide layer having arefractive index higher than that of the substrate 1 and formed from afilm of an optical functional material KTa_(x)Nb_(1-x)O₃ (0<x<1), 3 aninput optical signal, 4 an electrode, 5 an output optical signal, and 6an overcladding layer (cover layer) covering the waveguide layer andhaving a refractive index lower than that of the waveguide layerKTa_(x)Nb_(1-x)O₃ film 2.

The input optical signal 3 is transmitted into the KTa_(x)Nb_(1-x)O₃film 2. The KTa_(x)Nb_(1-x)O₃ film 2 changes its optical property by anexternal voltage signal applied to the electrode 4. Thus, the opticalsignal is modulated by the film's optical property change as it passesthrough the KTa_(x)Nb_(1-x)O₃ film 2. The modulated optical signal istaken out as the output optical signal 5.

The waveguide layer may use as an alternative an optical functionalmaterial K_(1-x)Li_(v)Ta_(x)Nb_(1-x)O₃ (1<x<1, 0<v≦0.5).

Although in the following embodiments only the manufacturing methods wetested will be described, it is quite obvious to persons skilled in theart that, for the individual material region manufacturing processesclassified earlier, known thin film manufacturing techniques, such asliquid phase epitaxy, physical deposition, chemical vapor deposition andsol-gel processing, can be applied and that the known masking andetching techniques can be applied to the forming of individualstructures.

Embodiment 1-1

First, the manufacturing process 1 will be explained. In thisembodiment, the liquid phase epitaxy capable of forming a single crystalfilm with high quality was adopted as the method of depositing a highquality KTa_(x)Nb_(1-x)O₃ film on the substrate 1. A KTa_(x)Nb_(1-x)O₃(0≦x≦1) substrate, a MgO substrate, a MgAl₂O₄ substrate and a NdGaO₃substrate were used for the substrate 1. As the buffer layer(undercladding layer) were used a semiconductor Si substrate, a GaAssubstrate and an InP substrate, which were formed by depositing suchmaterials as SiO₂, KTa_(x)Nb_(1-x)O₃ (0≦x≦1), MgO, MgAl₂O₄ and NdGaO₃.

To prevent a possible contamination, the KTa_(x)Nb_(1-x)O₃ film 2 wasformed by using potassium oxide and KTa_(x)Nb_(1-x)O₃ oxide as a solventand a solute, respectively, and by using a self-flux method. As thepotassium oxide solvent, a mixture of KVO₃ and K₂O (KVO₃=30-70 mol %) orK₂CO₃ carbonate was used. When a KTa_(y)Nb_(1-y)O₃ (0≦y≦1) substrate wasused, a material with x (0<x<1) composition different from the substratecomposition was selected so that there was a difference in refractiveindex between the substrate and the waveguide layer. Hence, in thefollowing description the material used as the waveguide layer and thematerial used as the substrate 1 are shown to have compositions ofKTa_(x)Nb_(1-x)O₃ (0<x<1) and KTa_(y)Nb_(1-y)O₃ (0≦y≦1), respectively.

To change the characteristic of the waveguide layer, 0-10 mol % of LiCO₃was added to KTa_(x)Nb_(1-x)O₃ (0<x<1). The solute concentration withrespect to the solvent was set to 30-50 mol %, a concentration rangewhere the object material KTa_(x)Nb_(1-x)O₃ is shown in a phase diagramto precipitate as an initial crystal. The film deposition temperaturewas set at 0-10° C. supercooled from a solid-solution equilibriumtemperature of 1,050-1,360° C. determined from the liquidus of the phasediagram and the concentration of the solute used. This temperature wasused considering the fact that a low film deposition rate constitutesone of conditions for forming a high quality film. However, there wasalso a case where a growth rate with a larger supercooling had to beused when considering a lattice matching between the KTa_(x)Nb_(1-x)O₃and the substrate material used and a reactivity between the solutionand the substrate used.

The film deposition rate achieved was around 1 μm/min. The filmdeposition time was determined from the precalculated deposition rateand the desired film thickness.

The crystal quality of the KTa_(x)Nb_(1-x)0₃ film deposited to athickness of 2 μm was best when the substrate used the same material asthe film material, i.e., the material that satisfies the homo epitaxialcondition. The KTa_(x)Nb_(1-x)O₃ film thus formed has an optical qualityof 0.10 dB/cm in terms of optical transmission loss. TheKTa_(x)Nb_(1-x)O₃ film was verified by the X-ray diffraction method tobe oriented in a <100> axis direction.

Embodiment 1-2

Next, the manufacturing process 2 will be explained. Photolithographywas used to process the KTa_(x)Nb_(1-x)O₃ film to form a waveguide layerof a ridge type optical waveguide. A resist was applied to the thin filmthus formed and was exposed and developed by using a mask for a 2 μmwide waveguide. The material was then etched by an ion milling methodand the residual resist was removed, thereby forming a waveguide layerof the ridge type waveguide. The waveguide layer is nearly a 2 μm squareand an observation of the side wall using a SEM (scanning electronmicroscope) found no significantly roughened surface.

The measurement of loss of this ridge type waveguide at a wavelength of1.55 μm showed a loss value of 0.99 dB/cm, which means that thewaveguide layer formed is good enough so that undulations of the surfaceas a result of processing can be neglected.

Embodiment 1-3

Next, the manufacturing process 3 will be explained. The electrodematerial is preferably a metal or conductive oxide highly chemicallystable with the KTa_(x)Nb_(1-x)O₃ film. In this embodiment, we willdescribe a result of manufacture with Au used as an electrode material.

In manufacturing an Au electrode of a shape according to the design,techniques commonly used in the semiconductor integrated circuitmanufacturing process were applied. More specifically, the Au thin filmdeposited by sputtering was processed by photolithography.

The techniques used in this manufacturing process 3 are common andtherefore their explanations are omitted.

Embodiment 1-4

The material used for the cover layer 6 was chosen from among suchoxides as KTa_(u)Nb_(1-u)O₃ (0≦u≦1), MgO, MgAl₂O₄ and NdGaO₃, and apolymer that retards degradation of the already fabricated waveguide andelectrode structure. In this embodiment, we will describe a result offabrication obtained when a sputtering method with a low substratetemperature during evaporation was used to deposit KNbO₃.

For the fabrication of the cover layer 6 an opposed type ion sputteringapparatus was used. Nb and K₂CO₃ targets were mounted on one surfaceand, on the opposing surface 2-10 cm from the substrate, was mounted. Asan ambient gas a Xe gas was used at a pressure of 1×10⁻⁴ to 3×10⁻⁴ Torr.A voltage was applied between the targets and the substrate to producean energy of 400-800 eV for Nb ions and K₂CO₃ ions to deposit a film ofKNbO₃ cover layer at the substrate temperature of 500-700° C. The filmwas deposited to a thickness of 0.1 μm at a rate of 3 Å/min. The thinfilm thus obtained was verified to be KNbO₃ by the X-ray diffractionmethod.

The same technique as used in the manufacturing process 2 was used toopen holes in the upper surface of the electrode 4 to lead conductivewires into the electrode 4 formed by the manufacturing process 3.

The basic optical integrated circuit fabricated by the manufacturingprocess 1, manufacturing process 2, manufacturing process 3 andmanufacturing process 4 in that order was cut and its cross section wasobserved with a SEM, which revealed no significant structuraldeterioration. Further, the performance of the electrode 4 connectedwith conductive wires was evaluated using the input optical signal 3with a wavelength of 1.55 μm. It was confirmed that the wavelengthconversion device and the modulator had high performances, i.e., highefficiency and low noise, as expected from the design.

We have described a case where the waveguide layer of KTa_(x)Nb_(1-x)O₃(0<x<1) was formed on a substrate. In a general core-cladding structure,optical waveguides can of course be provided with a variety ofcharacteristics, not possible with the conventional techniques, byforming the core from KTa_(x)Nb_(1-x)O₃ (0<x<1).

Embodiment 2

FIG. 2 is a perspective view showing another fabrication of an opticalwaveguide applying the present invention. In this case, the waveguidestructure is a rectangular parallelepiped extending along the substrate.In the following, the rectangular parallelepiped structure film isdescribed to be fabricated by a thin film growth method. In the figure,reference numeral 11 represents a substrate, 12 a KTa_(x)Nb_(1-x)O₃film, 13 an input optical signal, 14 an electrode, 15 an output opticalsignal, and 16 a groove. The input optical signal 13 is transmitted intothe KTa_(x)Nb_(1-x)O₃ film 12. The KTa_(x)Nb_(1-x)O₃ film 12 changes itsoptical property by an external voltage signal applied to the electrode4. Thus, the optical signal is modulated by the film's optical propertychange as it passes through the KTa_(x)Nb_(1-x)O₃ film 12. The modulatedoptical signal is taken out as the output optical signal 15.

To deposit a high quality KTa_(x)Nb_(1-x)O₃ film on the substrate, aliquid phase epitaxy capable of forming a high quality single crystalfilm was selected as a film deposition method. The substrate materialwas chosen by considering mainly a lattice matching, a basic conditionfor the epitaxial growth. The substrate was chosen from among aKTa_(x)Nb_(1-x)O₃ (0≦x≦1) substrate, a MgO substrate, a MgAl₂ substrateand a NdGaO₃ substrate.

Further, a semiconductor Si substrate, GaAs substrate or InP substratedeposited with SiO₂, KTa_(x)Nb_(1-x)O₃ (0≦x≦1), MgO, MgAl₂O₄ or NdGaO₃was also used. A photolithography method commonly used in thefabrication of semiconductor integrated circuits, such as masking andetching or masking and ion milling, was used to pattern on the substratethe groove 6, 0.1-0.2 μm wide and 0.01 μm or more deep, along a centerline of an area where the waveguide is to be formed.

To prevent a possible, the film was formed by using potassium oxide andKTa_(x)Nb_(1-x)O₃ oxide as a solvent and a solute, respectively, andalso using a self-fluxing method. As the potassium oxide solvent, amixture of KVO₃ and K₂O (KVO₃=30-70 mol %) or K₂CO₃ carbonate was used.When a KTa_(x)Nb_(1-x)O₃ (0≦x≦1) substrate was used, a materialKTa_(x′)Nb_(1-x′)O₃ with x′ (0≦x′≦1) composition different from thesubstrate composition was selected so that there was a difference inrefractive index between the substrate and the waveguide. Further, 0-10mol % of LiCO₃ was also added as an additive.

The above process resulted in a thin film with KTa_(x)Nb_(1-x)O₃replaced with K_(1-y) Li_(y)Ta_(x)Nb_(1-x)O₃ (0≦x≦1, 0≦y≦0.5; x and yare compositions). The solute concentration with respect to the solventwas set to 30-50 mol %, a concentration range where the object materialKTa_(x′)Nb_(1-x′)O₃ is shown in a phase diagram to precipitate as aninitial crystal. The film deposition temperature was set at 0-10° C.supercooled from a solid-solution equilibrium temperature of1,050-1,360° C. determined from the liquidus of the phase diagram andthe concentration of the solute used. This temperature was usedconsidering the fact that a low film deposition rate constitutes one ofconditions for forming a high quality film. However, there was also acase where a growth rate with a larger supercooling had to be used whenconsidering a lattice matching between the KTa_(x′)Nb_(1-x′)O₃ and thesubstrate material used and a reactivity between the solution and thesubstrate used. The film deposition rate achieved was around 1 μm/min.The film deposition time was determined from the precalculateddeposition rate and the desired film thickness.

The crystal quality of the KTa_(x′)Nb_(1-x′)O₃ film deposited to athickness of 2 μm was best when the substrate was formed from the samematerial or constitutional elements as the film material, i.e., thematerial that satisfies the homo epitaxial condition. TheKTa_(x′)Nb_(1-x′)O₃ film thus formed has an optical quality of 0.10dB/cm in terms of optical transmission loss at a wavelength of 1.55 μm.The KTa_(x′)Nb_(1-x′)O₃ film was verified by the X-ray diffractionmethod to be oriented in a <100> axis direction.

As for the structure of the waveguide obtained, it extends along thegroove and has a rectangular cross section 2 μm wide with the groove inthe substrate as a center. The observation using a SEM (scanningelectron microscope) showed that the sidewall surfaces of the waveguidehad microsteps made up of {100} surfaces with a better planarity thanthat of the sidewall surfaces of the waveguide fabricated by theconventional photolithography. Strictly speaking, its cross section hadprojections in the groove region at positions of crystal growth nucleibut since the projections were small compared with the rectangularcross-sectional area, their influence on the transmitted light wassmall.

Rather than providing the groove structure on the substrate, forming agroove or holes where crystal growth nuclei were to be created was ableto produce the similar effect.

FIG. 3 shows a substrate formed with a groove at positions of crystalgrowth nuclei for the KTa_(x)Nb_(1-x)O₃ crystal. In the figure,reference numeral 11 denotes the substrate and 16 the groove.

FIG. 4 shows a substrate formed with holes at positions of crystalgrowth nuclei for the KTa_(x)Nb_(1-x)O₃ crystal. In the figure,reference numeral 11 denotes the substrate and 17 the holes.

Instead of processing the substrate, forming a groove or holes in theelectrode layer on the substrate was able to produce the similar effect.

FIG. 5 shows a substrate having an electrode layer formed with holes atpositions of crystal growth nuclei for the KTa_(x)Nb_(1-x)O₃ crystal.FIG. 6 is a cross section taken along the line VI-VI of FIG. 5. In thefigure, reference number 11 denotes the substrate and 18 the holedelectrode layer.

Embodiment 3 Embodiment 3-1

Next, a method of manufacturing a diffused waveguide by diffusing Liions in a crystal of the core formed from a crystal material ofKTa_(x)Nb_(1-x)O₃ composition will be explained.

A KTN crystal plate 10 mm square and 0.5 mm thick which was opticallypolished on both sides was put in a platinum boat together with LiNO₃powder. They were heated in the atmosphere at 300° C., 400° C., 500° C.and 550° C. for 10 hours each. LiNO₃ with a melting point of 261° C.melted when heated and the KTN crystal plate was soaked in the LiNO₃liquid. Then, the specimen was cooled in a furnace down to a roomtemperature and then the boat was taken out. In either case, LiNO₃ wasin a solid form when taken out. Hence, the boat was washed with purewater and the crystal substrate was taken out. The diffusion state of Liions in the specimen was analyzed by the SIMS (secondary ion massspectrometry).

Of the specimens described above, the one heat-treated at 550° C.appeared opaque white at the surface and partly flaked. This isconsidered due to the phenomenon in which the Li ion concentration atthe crystal surface becomes locally too high causing a densitydifference with respect to the KTN crystal. Hence, it is desired thatthe ion diffusion be performed at or below 500° C.

In this embodiment, a Li ion diffusion profile obtained from the 500° C.heat treatment is shown in FIG. 7. As can be seen from FIG. 7, it isverified that the heat treatment in LiNO₃ has resulted in the iondiffusion. A temperature increase caused an increase in the ionconcentration and the diffusion distance. The crystal diffused with Liwas heated in the atmosphere at 700° C. for 10 hours to perform aninternal diffusion of Li ions.

A SIMS analysis result for Li ions is shown in FIG. 8. FIG. 9 shows arefractive index distribution estimated by the IWKB method using aneffective refractive index measured in each mode by a prism coupling. Ascan be seen from FIG. 8 and FIG. 9, a moderately curved refractive indexdistribution is formed. A relative index difference on the surfaceportion is 1% or higher and it is apparent that the Li diffusion canimplement an index difference large enough to function as a waveguide.

Further, while in this embodiment the internal diffusion was performedin the atmosphere, it may be done in the presence of oxygen, inert gas,water vapor or a mixture of these gases to produce the similar effects.

Using the photolithography, a Pt mask pattern was formed on the KTNcrystal surface and a linear portion 1 μm wide not deposited with Pt wasformed. The crystal was subjected to the Li diffusion in the same way asin Embodiment 3-1. The heat treatment in LiNO₃ was performed at 400° C.for 10 hours, after which the internal diffusion was carried out in thepresence of oxygen at 700° C. for 5 hours. Then, the Pt mask was etchedaway by nitric acid. The crystal used in this embodiment is 20 mm squareand 0.5 mm thick.

Therefore, this method can form a linear waveguide 20 mm long. Thewaveguide thus formed was a single-mode waveguide with a mode fielddiameter of 8 μm at a wavelength of 1.55 μm. After being applied withanti-reflection coating at both end faces, the waveguide was aligned andconnected with single-mode fibers using UV resin. The insertion lossmeasured at the wavelength of 1.55 μm was 2.5 dB and the waveguide losstaking the losses at end faces into account was 0.1 dB/cm.

As described above, with the method of Embodiment 3-1 of this invention,it is seen that a single-mode waveguide with small losses can befabricated. By changing the diffusion temperature in the range ofbetween 300° C. and 500° C. and the diffusion time in the range ofbetween 2 and 100 hours, it was found possible to change the mode fielddiameter arbitrarily.

Embodiment 3-2

The Li diffusion was performed under the same condition as in Embodiment3-1 and Pt was etched, after which the crystal was heated in a liquid ofmelted KNO₃ at 400° C. for five hours. When the crystal containing Liions is heated in the liquid of melted KNO₃, Li ions diffuse into theKNO₃ liquid from those portions of the crystal surface where the Liconcentrations are high, and K ions in the KNO₃ liquid diffuse into thecrystal. As a result, near the surface of the crystal, Li ions arereplaced with K ions, reducing the Li ion concentrations.

Then, the specimen was cooled down to a room temperature and thesolidified KNO₃ was washed away to recover the crystal substrate. Thecrystal substrate was then heated in the atmosphere at 650° C. for 10hours to obtain a crystal formed with a waveguide.

The Li ion distribution in the waveguide manufactured according to thismethod was measured by the SIMS in the depth direction and in thehorizontal direction. The result of measurement is shown in FIG. 10. Asshown in FIG. 10, in addition to the method of Embodiment 3-1 describedabove, performing the heat treatment in KNO₃ made it possible tofabricate a waveguide with an almost symmetrical ion distribution. Thiswaveguide exhibited no difference in light transmission characteristicbetween a TE mode and a TM mode. With the method of this embodiment, adiffused waveguide was obtained which has no polarization dependency.Its waveguide loss as measured by a technique similar to that used inEmbodiment 3-1 was 0.13 dB/cm and even the heat treatment in KNO₃resulted in no significant increase in loss. It is therefore found thatthe method of this embodiment is effective in making the waveguideindependent of polarization. Reference number 21 denotes the surface, 22the Li ion diffusion area (core), and 23 the cladding.

Embodiment 3-3

On the linear waveguide fabricated by the method of Embodiment 3-1 anelectrode pattern with a period of about 12 μm was formed. The oppositesurface was deposited with gold to form a lower electrode. The crystalwas placed on a Peltier element so that its temperature can becontrolled. The cutoff wavelength for the multimode is 0.7 μm and, forlonger wavelengths, the waveguide functions as a single-mode waveguide.The length of the waveguide manufactured was 3 cm and the loss of thewaveguide was 0.15 dB/cm.

FIG. 11 shows the fabrication of a device manufactured in thisembodiment. An electrode pitch corresponds to a grating pitch thatrealizes a quasi-phase matching required to perform a wavelengthconversion on a 1.55 μm band with a 0.775 μm light used as a pump light.In this case, the electrode pitch is 12 μm. A voltage corresponding to 1kV/cm was applied to the electrode; using polarization maintainingfibers, a signal light of 1.54 μm and a pump light of 0.775 μm weresimultaneously launched into the device; and an output light wasmeasured using an optical spectrum analyzer. Reference number 34designates a Li diffused waveguide, 35 an upper electrode, 36 a lowerelectrode, and 37 a Peltier element.

FIG. 12 shows a spectrum of light after it was wavelength-converted,with [a] representing a signal light, [b] a second-order diffractedlight of the pump light and [c] a converted light. As can be seen fromFIG. 12, the conversion efficiency was calculated to be about 20 timesthat of the quasi-phase matching device of LiNbO₃. In this wavelengthconversion, the light is confined in the diffused core and thenonlinearity coefficient of the core determines the efficiency of thewavelength conversion device. As shown in this embodiment, it is foundthat the nonlinearity of the KTN waveguide with diffused Li is very highand is not degraded before or after the Li diffusion.

Embodiment 4

The present invention is characterized in that diketone complex as astarting material of K is used to fabricate a crystal film ofKTa_(1-x)Nb_(x)O₃ (0<x<1) (hereinafter referred to simply as KTN) andthat metal β-diketone complexes-as starting material of K and Li areused to fabricate crystal films of K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ (0<x<1and 0<y<1) (referred to simply as KLTN). The β-diketone complex of K andβ-diketone complex of Li are defined in general expressions (1) and (2),respectively:

(In the above expressions, R is an alkyl group with a carbon number ofbetween 1 and 7; R′ is an alkyl group or C_(n)F₂₊₁; and n=1 to 3)

As can be seen from the general expressions (1) and (2), the metalβ-diketone complexes have a structure in which an organic substancecoordinates with metal ions through oxygen. This structure is stabilizedby electrons becoming unlocalized in a six-membered ring consisting ofoxygen and carbon including K or Li.

The electron state of the six-membered ring can be controlled by the twokinds of substituents R and R′ bonding to carbon elements. Thesesubstituents determine a three-dimensional structure, so if they arestructured to enclose K or Li, the volatility can be increased. The useof the metal β-diketone complexes can vaporize K or Li at temperaturesbelow 300° C. to secure a vapor pressure necessary for the CVD method.

In this compound, however, the volatilization and decompositiongenerally conflict with each other, so it is important to properlyselect the substituents R and R′ to improve the stability fordecomposition. To secure the stability against decomposition it isdesired that the substituents be alkyl groups with a large carbonnumber. On the other hand, to increase the volatility it is effective toreplace hydrogen of the alkyl group with fluorine. In this invention,therefore, when an emphasis is placed on the thermal stability againstdecomposition, an alkyl group or t-butyl group with a long normal chainis used. When the volatility is emphasized, C_(n)F_(2n+1) is used. Instriking a balance between stability and volatility, it is effective touse the alkyl group as one substituent R and the fluorine-replacedalkyl-group as the other R′.

More specifically, preferred β-diketone complexes of K include, but notlimited to, those complexes having as ligands2,2-dimethyl-3,5-octanedione,2,2-dimethyl-6,6,6-trifuoro-3,5-hexanedione,5,5,5-trifluoro-2,4-pentanedione,2,2-dimethyl-6,6,7,7,7-pentafluoro-3,5-heptanedione, and2,2-dimethyl-6,6,7,7,8,8,8-heptanefluoro-3,5-octanedione. Preferredβ-diketone complexes of Li include, but not limited to, those complexeswith 2,6,6-tetramethyl-3,5-heptanedione as ligands.

The method of manufacturing a KTN crystal film of this inventionintroduces, as a gas flow into a reaction system, the β-diketone complexof K described above, a gaseous compound and/or a volatile compound ofTa, which is one of metal elements making up the crystal film, a gaseouscompound and/or a volatile compound of Nb, and an oxygen-containing gasthat works as an oxidizing agent. In this reaction system a substrate isprovided and the introduced components are reacted in gas phase or onthis substrate to form a KTN crystal film on the substrate.

The method of manufacturing a KLTN crystal film of this inventionintroduces, as a, gas flow into a reaction system, the β-diketonecomplexes of K and Li described above, a gaseous compound and/or avolatile compound of Ta, which is one of metal elements making up thecrystal film, a gaseous compound and/or a volatile compound of Nb, andan oxygen-containing gas that works as an oxidizing agent. This reactionsystem is provided with a substrate, and the introduced components arereacted in gas phase or on this substrate to form a KLTN crystal film onthe substrate.

Among preferred gaseous and/or volatile compounds of Ta used in thisinvention are alkoxide such as Ta(OC₂H₅)₅ and halide TaCl₅. Preferredgaseous and/or volatile compounds of Nb include alkoxide such asNb(OC₂H₅)₅ and halide NbCl₅.

The oxygen-containing gas is preferably a gas containing oxygen, or agas containing oxygen and at least one of hydrogen and nitrogen. Whenfluorinated alkyl is used as a substituent of β-diketone complex of Kand/or β-diketone complex of Li, it is preferred that anoxygen-containing gas containing hydrogen be used as a fluorine getter.

Among possible substrates for use in this invention are SrTiO₃, SiO₂,MgO, MgAl₂O₄, NdGaO₃, KTa_(1-x)Nb_(x)O₃, K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃,and K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃. The temperature of the substrateduring reaction is preferably in the range of 400-1,200° C. because theKTN or KLTN crystal structure produced in this temperature range ishomogeneous.

Further, since the β-diketone complex of K and β-diketone complex of Lihave their metal ions already bonded with oxygen, they have an advantageof being able to produce an oxide by thermal decomposition without usingan oxidizer. It should be noted, however, that an oxygen-containing gasis preferably introduced for preventing contamination by carbon.

With this method, a fast film deposition rate of 100-150 μm/hour isobtained. The crystal films of KTa_(1-x)Nb_(x)O₃ and/orK_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ fabricated in this manner have a nonlinearoptical effect and an electrooptical effect and can be used in opticalsignal processing devices for wavelength conversion, waveform shapingand optical amplification.

Embodiment 4-1

FIG. 13 is an outline of the CVD apparatus used in this embodiment. Theraw material of K used was K(DPM)(2,2,6,6-tetramethyl-3,5-heptanedionecomplex) which has t-butyl groups as both substituents. The Ta materialand Nb material used were Ta(OC₂H₅)₅ and Nb(OC₂H₅)₅, respectively.K(DPM) is a solid material while Ta(OC₂H₅)₅ and Nb(OC₂H₅ )₅ are liquidmaterials. These materials were introduced into independentlytemperature-controlled bubblers, i.e., a Ta material bubbler 41, a Nbmaterial bubbler 42 and a K material bubbler 43, andtemperature-controlled by heaters (not shown).

As a material carrier gas, argon was used for K(DPM) and, for other Taand Nb materials, oxygen was used. The material temperature was set at200° C. for K(DPM), 142° C. for Ta(CO₂H₅)₅ and 145° C. for Nb(OC₂H₅)₅.The amount of material supplied was adjusted by the carrier gas flow.The piping temperature was controlled at 205° C. to prevent a possiblecondensation of the material. After the material gases were mixed in amixer 44, they were introduced into a reaction tube 45. The pressure inthe apparatus was reduced to 1.3 kPa (10 Torr), and the substrate 47 washeated by an external heater (electric furnace) 46 to 600° C., 700° C.,800° C., 900° C., 1,000° C. and 1,100° C. SrTiO₃ was used for thesubstrate. Reference numeral 41 denotes the Ta material bubbler, 42 theNb material bubbler, 43 the K material bubbler, and 48 a rotary pump.

The carrier gas was controlled so that the composition of the crystalwas KTa_(0.65)Nb_(0.35)O₃. The films were deposited to a thickness of2.0 μm. The crystal films formed at different temperatures describedabove were observed by a SEM and their crystal phases were identified bythe X-ray diffraction. The light transmission losses at the wavelengthof 1.55 μm were measured by the prism coupling, and the homogeneity ofeach crystal film was measured by measuring the strength distribution ofa second harmonic generation. The measurement results are shown inTable 1. TABLE 1 Light Deposi- Average trans- Substrate tion grainmission tempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystalstate (μm) (dB/cm) ity 600 0.3 Amorphous — 0.08 Excellent *600 —Polycrystalline  7 0.1 Excellent 700 0.5 Polycrystalline 10 0.1Excellent 800 0.9 Polycrystalline 15 0.1 Excellent 900 1.5Polycrystalline 25 0.1 Excellent 1,000 2.5 Single crystal — 0.1Excellent 1,100 5.0 Single crystal — 0.1 Excellent*600 After the film was formed at 600° C., it was heat-treated for twohours at 1,000° C. in the air.

The KTN film fabricated at a substrate temperature of 600° C. waschecked by the X-ray diffraction and found to be amorphous. Its lighttransmission loss was 0.08 dB/cm, which is sufficiently low for awaveguide film. The deposition rate was 0.3 μm/min.

This film was heat-treated for two hours at 1,000° C. in the air forcrystallization to produce a polycrystalline film. The X-ray diffractionshowed that after two hours of heat treatment at 1,000° C. in theatmosphere, the film was oriented in the direction of the substrateSrTiO₃. The SEM observation found that the average grain diameter was 7μm. The light transmission loss of this film was 0.1 dB/cm and there wasno significant increase in the scattering loss due to crystallization.Even with an incident He—Ne laser beam, no light scattering was observedat grain boundaries.

When the substrate temperature was set at 700° C., 800° C. and 900° C.,polycrystalline films oriented in the direction of the substrate wereobtained. The deposition rates at these temperatures-were 0.5 μm/min.0.9 μm/min and 1.5 μm/min, respectively. It is found that the graindiameter of the crystal film increases with the temperature. At thetemperature of 900° C. the average grain diameter reached 25 μm. Thelight transmission losses of these polycrystalline films were around 0.1dB/cm and the films were optically homogeneous.

For the substrate temperature of 1,000° C., the SEM observation and theX-ray diffraction analysis found that a single crystal was obtained. Theoptical characteristic of this film was almost identical with that ofthe polycrystalline films but with a slightly lower scattering loss.

FIG. 14 is a graph showing a temperature-dependency of dielectricconstant of the crystal grown at the substrate temperature of 1,000° C.It is seen from this graph that the dielectric constant at around thephase transition temperature reaches as high as 30,000 and that thisfilm is homogeneous and exhibits nearly the same characteristics asthose of the bulk single crystals.

For the substrate temperature of 1,100° C., a single crystal film wasable to be formed. But the volatilization of K₂O was remarkable and thusit was necessary to increase the amount of supply of K(DPM).

Embodiment 4-2 to 4-7

Crystal films were formed at predetermined temperatures (600, 700, 800,900, 1,000 and 1,100° C.) in a manner similar to Embodiment 4-1, exceptthat the following materials were used for the substrate instead ofSrTiO₃ used in Embodiment 4-1: SiO₂ (Embodiment 4-2), MgO (Embodiment4-3), MgAl₂O₄ (Embodiment 4-4), NdGaO₃ (Embodiment 4-5),KTa_(1-x)Nb_(x)O₃ and K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ (Embodiment 4-6),and K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ (Embodiment 4-7).

The crystal films thus formed were subjected to examinations similar tothose of Embodiment 4-1, i.e., identification of crystal phase andmeasurement of crystal grain diameter, light transmission loss andhomogeneity. The results of examinations are similar to those ofEmbodiment 4-1 and shown in Table 2 (Embodiment 4-2), Table 3(Embodiment 4-3), Table 4 (Embodiment 4-4), Table 5 (Embodiment 4-5),Table 6 (Embodiment 4-6), and Table 7 (Embodiment 4-7). TABLE 2 LightDeposi- Average trans- Substrate tion grain mission tempera- rate dia.loss Homogene- ture (° C.) (μm/min) Crystal state (μm) (dB/cm) ity 6000.3 Amorphous — 0.09 Excellent 700 0.5 Amorphous — 0.08 Excellent 8001.0 Amorphous — 0.08 Excellent 900 1.5 Amorphous — 0.09 Excellent 1,0002.6 Polycrystalline  5 0.12 Excellent 1,100 5.1 Polycrystalline 10 0.11Good

TABLE 3 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.3 Amorphous — 0.09 Excellent 700 0.5Polycrystalline  5 0.12 Excellent 800 1.0 Polycrystalline  7 0.13Excellent 900 1.5 Polycrystalline 10 0.12 Excellent 1,000 2.6 Singlecrystal — 0.12 Excellent 1,100 5.0 Single crystal — 0.11 Good

TABLE 4 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.3 Amorphous — 0.09 Excellent 700 0.5Polycrystalline 5 0.10 Excellent 800 1.0 Polycrystalline 7 0.11Excellent 900 1.5 Single crystal — 0.10 Excellent 1,000 2.5 Singlecrystal — 0.10 Excellent 1,100 5.0 Single crystal — 0.09 Excellent

TABLE 5 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.3 Amorphous — 0.08 Excellent 700 0.5Polycrystalline 6 0.11 Excellent 800 1.1 Polycrystalline 8 0.11Excellent 900 1.5 Polycrystalline 15  0.10 Excellent 1,000 2.6 Singlecrystal — 0.10 Excellent 1,100 5.1 Single crystal — 0.09 Excellent

TABLE 6 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.3 Amorphous — 0.08 Excellent 700 0.6Polycrystalline  7 0.11 Excellent 800 1.1 Polycrystalline 10 0.10Excellent 900 1.5 Single crystal — 0.10 Excellent 1,000 2.6 Singlecrystal — 0.10 Excellent 1,100 5.2 Single crystal — 0.09 Excellent

TABLE 7 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.3 Amorphous — 0.08 Excellent 700 0.5Polycrystalline 6 0.10 Excellent 800 1.1 Polycrystalline 9 0.10Excellent 900 1.5 Single crystal — 0.10 Excellent 1,000 2.6 Singlecrystal — 0.10 Excellent 1,100 5.0 Single crystal — 0.10 Excellent

[Embodiment 4-8 to 4-12

Crystal films were formed at predetermined temperatures (600, 700, 800,900, 1,000 and 1,100° C.) in a manner similar to Embodiment 4-1, exceptthat the ligands of the β-diketone complex as the K material were2,2-dimethyl-3,5-octanedione (Embodiment 4-8),2,2-dimethyl-6,6,6-trifluoro-3,5-hexandione (Embodiment 4-9),5,5,5-trifluoro-2,4-pentanedione (Embodiment 4-10),2,2-dimethyl-6,6,7,7,7-pentafluoro-3,5-heptanedione (Embodiment 4-11),2,2-dimethyl-6,6,7,7,8,8,8-heptanefluoro-3,5-octanedione (Embodiment4-12).

The crystal films thus formed were subjected to examinations similar tothose of Embodiment 4-1, i.e., identification of crystal phase andmeasurement of crystal grain diameter, light transmission loss andhomogeneity. In these Embodiments 4-8 to 4-12, the crystal filmsobtained have characteristics similar to those of Embodiment 4-1. When amaterial containing fluorine was used (Embodiments 4-9, 4-10, 4-11,4-12), there was a decrease in the deposition rate. However, introducingH₂O into the reaction system prevented the deposition rate reduction.

The results of measurements are shown in Table 8 (Embodiment 4-8), Table9 (Embodiment 4-9), Table 10 (Embodiment 4-10), Table 11 (Embodiment4-11), and Table 12 (Embodiment 4-12). TABLE 8 Light Deposi- Averagetrans- Substrate tion grain mission tempera- rate dia. loss Homogene-ture (° C.) (μm/min) Crystal state (μm) (dB/cm) ity 600 0.3 Amorphous —0.08 Excellent 700 0.5 Polycrystalline 10 0.10 Excellent 800 1.0Polycrystalline 15 0.10 Excellent 900 1.5 Polycrystalline — 0.10Excellent 1,000 2.5 Single crystal — 0.10 Excellent 1,100 5.0 Singlecrystal — 0.09 Excellent

TABLE 9 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.15 Amorphous — 0.08 Excellent 700 0.25Polycrystalline 12 0.10 Excellent 800 0.5 Polycrystalline 17 0.10Excellent 900 0.7 Polycrystalline — 0.10 Excellent 1,000 1.2 Singlecrystal — 0.10 Excellent 1,100 2.3 Single crystal — 0.09 Excellent

TABLE 10 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.12 Amorphous — 0.08 Excellent 700 0.25Polycrystalline 13 0.10 Excellent 800 0.4 Polycrystalline 17 0.10Excellent 900 0.6 Polycrystalline — 0.10 Excellent 1,000 1.2 Singlecrystal — 0.10 Excellent 1,100 2.2 Single crystal — 0.09 Excellent

TABLE 11 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.11 Amorphous — 0.08 Excellent 700 0.21Polycrystalline 13 0.10 Excellent 800 0.39 Polycrystalline 19 0.10Excellent 900 0.8 Polycrystalline — 0.10 Excellent 1,000 1.2 Singlecrystal — 0.10 Excellent 1,100 2.3 Single crystal — 0.09 Excellent

TABLE 12 Light Deposi- Average trans- Substrate tion grain missiontempera- rate dia. loss Homogene- ture (° C.) (μm/min) Crystal state(μm) (dB/cm) ity 600 0.11 Amorphous — 0.08 Excellent 700 0.2Polycrystalline 12 0.10 Excellent 800 0.35 Polycrystalline 19 0.10Excellent 900 0.8 Polycrystalline — 0.10 Excellent 1,000 1.3 Singlecrystal — 0.10 Excellent 1,100 2.5 Single crystal — 0.09 Excellent

Embodiment 4-13

Crystal films were fabricated at predetermined temperatures (600, 700,800, 900, 1,000 and 1,100° C.) in a manner similar to Embodiment 4-1,except that Li(DPM) was used in addition to K(DPM) as the initialmaterial and that TaCl₅ and NbCl₅ were also used. The compositions ofthese films thus formed were K_(0.9)Li_(0.1)Ta0.65Nb_(0.35)O₃. Thesecrystal films were subjected to examinations similar to those ofEmbodiment 4-1, i.e., identification of crystal phase and measurement ofcrystal grain diameter, light transmission loss and homogeneity. Theresults of measurements are shown in Table 13. TABLE 13 Light Deposi-Average trans- Substrate tion grain mission tempera- rate dia. lossHomogene- ture (° C.) (μm/min) Crystal state (μm) (dB/cm) ity 600 0.28Amorphous — 0.08 Excellent 700 0.48 Polycrystalline 12 0.10 Excellent800 0.85 Polycrystalline 19 0.10 Excellent 900 1.2 Polycrystalline —0.10 Excellent 1,000 2.2 Single crystal — 0.10 Excellent 1,100 3.8Single crystal — 0.09 Excellent

The measurement result indicates that the crystal films have crystalstates and transparent characteristics almost similar to those ofEmbodiment 4-1 and that this method can produce a high quality KLTNcrystal.

FIG. 15 shows a temperature.-dependency of dielectric constant of thecrystal film formed at 1,000° C. From the measurement of dielectricconstant it is evident that a homogeneous film was produced.

Embodiment 4-14

FIG. 16A and FIG. 16B illustrate a fabrication of a wavelengthconversion device manufactured in this embodiment. FIG. 16A is aperspective view of the wavelength conversion device and FIG. 16B is across-sectional view taken along the line XVIB-XVIB of FIG. 16A.

A SiO₂ substrate 54 with a lower electrode 50 of Au formed byevaporation was heated to 900° C. and deposited with a KTN crystal filmto a thickness of 5 μm in a manner similar to that of Embodiment 4-1. Onthe KTN crystal film a KLTN crystal film was formed to a thickness of0.4 μm by the method of embodiment 4-2. Both of the crystal films werepolycrystalline with a grain diameter of 15 μm. The KLTN crystal filmwas processed by photolithography into a ridge waveguide 52 0.4 μm wide.Then, a KTN crystal film was formed over the entire surface of thesubstrate by the method of Embodiment 4-1. This KTN crystal film wasgrown over the KLTN crystal film to a thickness of 3 μm. In this way, aKLTN crystal film waveguide enclosed by the KTN crystal film 51 wasobtained.

The relative index difference of the manufactured waveguide is 2.5% andthe cutoff wavelength is 0.6 μm. For longer wavelengths the waveguidefunctions as a single-mode waveguide. The length of the waveguidefabricated was 3 cm and the light transmission loss of the waveguide0.15 dB/cm.

An upper electrode 53 was formed over the KTN crystal film byevaporating gold. An electrode pitch corresponds to a grating pitch thatrealizes a quasi-phase matching required to perform a wavelengthconversion on a 1.55 μm band with a 0.773 μm light used as a pump light.In this case, the electrode pitch is 12 μm. Hence, this waveguidefunctions as a wavelength conversion device.

In this way, a wavelength conversion device with electrodes as shown inFIG. 16 was fabricated. A voltage corresponding to 1 kV/cm was appliedto the electrode; using polarization maintaining fibers, a signal lightof 1.54 μm and a pump light of 0.773 μm were simultaneously launchedinto the device; and an output light was measured using an opticalspectrum analyzer.

FIG. 12 shows a spectrum of light after it was wavelength-converted. Inthe figure, [a] represents the wavelength of a signal light, [b] thewavelength of a second-order diffracted light of the pump light and [c]the wavelength of a converted light. FIG. 12 clearly indicates that thewavelength conversion is realized by the differential frequencygeneration. Further, the signal light and the converted light wereparametric-amplified and the gain of the converted light with respect tothe input signal light reaches as high as about 15 dB, which cannot berealized with the conventional LN wavelength conversion devices. As canbe seen from this diagram, the method of this invention makes itpossible to arrange in layer functional KTN or KTLN waveguides on a SiO₂substrate.

Embodiment 4-15

A wavelength conversion device was manufactured in a way similar to thatof Embodiment 4-14, except that the substrate temperature was set at1,000° C. Although the crystal formed was a single crystal as thesubstrate temperature was changed, characteristics obtained were similarto those of Embodiment 4-14.

The present invention has been described in detail with respect topreferred embodiments, and it will now be apparent from the foregoing tothose skilled in the art that changes and modifications may be madewithout departing from the invention in its broader aspects, and it isthe intention, therefore, in the appended claims to cover all suchchanges and modifications as fall within the true spirit of theinvention.

1-23. (canceled)
 24. A method of manufacturing a crystal film having acomposition of KTa_(1-x)Nb_(x)O₃ (0<x<1), the method comprising stepsof: introducing in the form of gas flows into a reaction system having asubstrate β-diketone complex of K (R is an alkyl group with a carbonnumber of 1 to 7, R′ is an alkyl group or C_(n)F_(2n+1), and n is 1 to3) expressed by a general formula (1) as a first initial materialcomponent,

at least one of a gaseous Ta compound and a volatile Ta compound as asecond initial material component, at least one of a gaseous Nb compoundand a volatile Nb compound as a third initial material component, and anoxygen-containing gas used as an oxidizer, and reacting these componentsin a gas phase or on the substrate to form a crystal ofKTa_(1-x)Nb_(x)O₃ on the substrate.
 25. A method of manufacturing acrystal film as claimed in claim 24, wherein the oxygen-containing gasis oxygen or a mixture gas of oxygen and at least one of hydrogen andnitrogen.
 26. A method of manufacturing a crystal film as claimed inclaim 25, wherein an energy necessary for the reaction is supplied fromat least one of heat, light and plasma.
 27. A method of manufacturing acrystal film as claimed in claim 24, wherein an energy necessary for thereaction is supplied from at least one of heat, light and plasma.
 28. Amethod of manufacturing a crystal film having a composition ofK_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ (0<x<1 and 0<y<1), the method comprisingsteps of: introducing in the form of gas flows into a reaction systemhaving a substrate β-diketone complex of K (R is an alkyl group with acarbon number of 1 to 7, R′ is an alkyl group or C_(n)F_(2n+1), and n is1 to 3) expressed by a general formula (1) as a first initial materialcomponent,

β-diketone complex of Li (R is an alkyl group with a carbon number of 1to 7, R′ is an alkyl group or C_(n)F_(2n+1), and n is 1 to 3) expressedby a general formula (2) as a second initial material component,

at least one of a gaseous Ta compound and a volatile Ta compound as athird initial material component, at least one of a gaseous Nb compoundand a volatile Nb compound as a fourth initial material component, andan oxygen-containing gas used as an oxidizer, and reacting thesecomponents in a gas phase or on the substrate to form a crystal ofKTa_(1-x)Nb_(x)O₃ on the substrate.
 29. A method of manufacturing acrystal film as claimed in claim 28, wherein the oxygen-containing gasis oxygen or a mixture gas of oxygen and at least one of hydrogen andnitrogen.
 30. A method of manufacturing a crystal film as claimed inclaim 29, wherein an energy necessary for the reaction is supplied fromat least one of heat, light and plasma.
 31. A method of manufacturing acrystal film as claimed in claim 28, wherein an energy necessary for thereaction is supplied from at least one of heat, light and plasma.
 32. Amethod of manufacturing a crystal film having a composition ofKTa_(1-x)Nb_(x)O₃ (0<x<1), the method comprising steps of: introducingin the form of gas flows into a reaction system having a substrateβ-diketone complex of K (R is an alkyl group with a carbon number of 1to 7, R′ is an alkyl group or C_(n)F_(2n+1), and n is 1 to 3) expressedby a general formula (1) as a first initial material component,

at least one of a gaseous Ta compound and a volatile Ta compound as asecond initial material component, and at least one of a gaseous Nbcompound and a volatile Nb compound as a third initial materialcomponent, and reacting these components in a gas phase or on thesubstrate to form a crystal of KTa_(1-x)Nb_(x)O₃ on the substrate.
 33. Amethod of manufacturing a crystal film as claimed in claim 32, whereinan energy necessary for the reaction is supplied from at least one ofheat, light and plasma.
 34. A method of manufacturing a crystal filmhaving a composition of K_(1-y)Li_(y)Ta_(1-x)Nb_(x)O₃ (0<x<1 and 0<y<1),the method comprising steps of: introducing in the form of gas flowsinto a reaction system having a substrate β-diketone complex of K (R isan alkyl group with a carbon number of 1 to 7, R′ is an alkyl group orC_(n)F_(2n+1), and n is 1 to 3) expressed by a general formula (1) as afirst initial material component,

β-diketone complex of Li (R is an alkyl group with a carbon number of 1to 7, R′ is an alkyl group or C_(n)F_(2n+1), and n is 1 to 3) expressedby a general formula (2) as a second initial material component,

at least one of a gaseous Ta compound and a volatile Ta compound as athird initial material component, and at least one of a gaseous Nbcompound and a volatile Nb compound as a fourth initial materialcomponent, and reacting these components in a gas phase or on thesubstrate to form a crystal of KTa_(1-x)Nb_(x)O₃ on the substrate.
 35. Amethod of manufacturing a crystal film as claimed in claim 34, whereinan energy necessary for the reaction is supplied from at least one ofheat, light and plasma.